Heterogeneous asymmetric hydrogenation of ethyl pyruvate on chirally modified Pt/Al2O3 catalyst with fixed-bed reactor

The enantioselective hydrogenation of ethyl pyruvate on the cinchonidine modified Pt/Al2O3 catalyst was investigated using a high-pressure reaction system with a fixed-bed reactor for the purpose to produce the,chiral product without separating the catalyst from the reaction system. The reaction was also investigated in a batch reactor for comparison. About 60% e. e. and 90% e. e. were obtained with the fixed-bed reactor and the batch reactor respectively, demonstrating the possibility for the heterogeneous asymmetric hydrogenation in the fixed-bed reactor. Some adsorbed chiral modifier, cinchonidine, can be slowly removed from the surface of Pt/Al2O3 under the continuous flow reaction, as a result, the e, e, values drops with the reaction time in the fixed-bed reactor. The enantio-selectivity is higher in the fixed-bed reactor, but lower in the batch reactor when ethanol was used as solvent than that when acetic acid as solvent. CO was used as molecular probe to characterize the adsorption of cinchonidine an the catalyst surface by IR spectroscopy, A red shift observed in IR spectra of coadsorbed CO with cinchonidine suggests that the cinchonidine adsorption is mainly through the pi -interaction with platinum surface and donating electron to the platinum surface.

The study of oxygen spillover and back spillover on Pt/TiO2 by a potential dynamic sweep method

Oxygen spillover and back spillover on Pt/TiO2 catalysts have been studied by a potential dynamic sweep method. The characteristics of I-V profiles of Pt/TiO2 electrodes in the three potential sweep regions are different from those of Pt and TiO2 electrodes. The catalytic role of Pt/TiO2 in oxygen spillover and back spillover is identified. It decreases, and the electrochemical oxygen adsorption (or desorption) increases with elevating temperature of hydrogen post-treatment of Pt/TiO2; to a certain extent (hydrogen post-treatment of Pt/TiO2 at 700 degrees C), the control step of oxygen electrode process (anodic oxidation or cathodic reduction) changes from oxygen diffusion to electrochemical oxygen adsorption or desorption, respectively. Increasing the amount of Pt supported on TiO2 enhances the processes of oxygen spillover and back spillover. (C) 1999 Elsevier Science B.V. All rights reserved.